对水笼团簇(H2O)6氢键的理论分析-凝聚态物理专业论文.docxVIP

哈尔滨工业大学理学硕士学位论文 哈尔滨工业大学理学硕士学位论文 -II- -II- Abstract Researchers have paid more and more attentions on the clathrate hydrate, because hydrogen molecules can be stored safely in it. The host structure of clathrate hydrate is a water cage which made up of hydrogen-bonded water molecules, and the guest molecules are stored in the cage. The cage of water hexamer has the minimum tree-dimension cage structure. To analyze the hydrogen bond in water cage will give more information about the hydrogen storing, the substance of hydrogen bond, and the interaction of hydrogen bond and H2O molecules. In this paper the ab initio method of molecular orbital theory is applied, the methods of HF, MP2, and CCSD(T) as well as larger baisis sets are used to investigate the water clusters (H2O)n, which form the simplest structure (H2O)2 to the complicated structure (H2O)6 . The analysis of the structure of water hexamer is emphasized, especially it’s vibrational frequencies, binding energy, and the interaction between two molecules The water dimer (H2O)2 is the smallest water cluster. In this thesis the interaction between two H2O molecules is analyzed particularly, and a new approximation method for analyzing the character of the interactions in (H2O)2 is established, which multipole moments are used to calculate the electrostatic interaction energy. The analysis indicates that the interaction of two H2O molecules in the water dimer is composed of the attraction and the repulsion, and the electrostatic effect occupies over 93% of the total attraction as well as other form effect (7%) such as covalent effect. In this thesis the structure of water cage cluster (H2O)6 is determined. The vibrational bending frequencies are blue-shifted by 29.47-114.11cm-1 with respect to the H2O molecule. It indicates that the hydrogen bond affects the vibrational frequencies, and the H2O molecules with dangling H atoms tend to have lower frequencies. The average binding energy of water cage cluster (H2O)6